Halogenated amide ester and internal electron donor with same

ABSTRACT

Disclosed are halogenated amide esters that are suitable as internal electron donors in procatalyst compositions. Ziegler-Natta catalyst compositions containing the present procatalyst compositions exhibit improved catalyst activity and/or improved catalyst selectivity and produce propylene-based olefins with broad molecular weight distribution.

CROSS REFERENCE TO RELATED APPLICATION

The present application is the national phase of PCT patent applicationSer. No. PCT/US2011/026029 filed Feb. 24, 2011, which claims the benefitof USSN 61/308,654 filed Feb. 26, 2010. The entire content of which isincorporated by reference herein.

BACKGROUND

The present disclosure relates to halogenated amide esters, andprocatalyst compositions and catalyst compositions containing the same.

Worldwide demand for olefin-based polymers continues to grow asapplications for these polymers become more diverse and moresophisticated. Olefin-based polymers with broad molecular weightdistribution (MWD), for example, find increasing applications inthermoforming; pipe-, foam-, blow-molding; and films. Known areZiegler-Natta catalyst compositions for the production of olefin-basedpolymers, particularly propylene-based polymers, with broad MWD.Ziegler-Natta catalyst compositions typically include a procatalystcomposed of a transition metal halide (i.e., titanium, chromium,vanadium) supported on a metal or metalloid compound, such as magnesiumchloride or silica, the procatalyst complexed with a cocatalyst such asan organoaluminum compound. Production of olefin-based polymers withbroad MWD produced by way of Ziegler-Natta catalysts, however, istypically limited to a single reactor process requiring rigorous processcontrol and/or a series reactor process requiring multiple reactors.

Given the perennial emergence of new applications for olefin-basedpolymers, the art recognizes the need for olefin-based polymers withimproved and varied properties. Desirable would be a Ziegler-Nattacatalyst composition that produces olefin-based polymer, andpropylene-based polymer in particular, with broad molecular weightdistribution (MWD) with less process constraints and less equipment.

SUMMARY

The present disclosure is directed to halogenated amide esters, and theuse of same in procatalyst and catalyst compositions. Catalystcompositions containing the halogenated amide ester find application inolefin polymerization processes. The present halogenated amideester-containing catalyst compositions have high catalyst activity, highselectivity, and produce propylene-based olefins with high isotacticityand broad molecular weight distribution.

In an embodiment, a halogenated amide ester is provided. The halogenatedamide ester has the structure (I) below.

R₁-R₆ are the same or different. Each of R₁-R₆ is selected fromhydrogen, a halogen, and an acyclic alkyl group having 1-20 carbonatoms. At least one of R₁-R₆ is an acyclic alkyl group. Ar₁ and Ar₂ arethe same or different. Each of Ar₁ and Ar₂ is selected from an arylgroup having 6-20 carbon atoms, and an arylalkyl group having 7-20carbon atoms. At least one of Ar₁ and Ar₂ is halogenated.

In an embodiment, a procatalyst composition is provided. The procatalystcomposition includes a combination of a magnesium moiety, a titaniummoiety and an internal electron donor. The internal electron donorincludes a halogenated amide ester. The halogenated amide ester has thestructure (I) below.

R₁-R₆ are the same or different. Each of R₁-R₆ is selected fromhydrogen, halogen, a hydrocarbyl group having 1-20 carbon atoms, and asubstituted hydrocarbyl group having 1-20 carbon atoms. Ar₁ and Ar₂ arethe same or different. Each of Ar₁ and Ar₂ is selected from an arylgroup having 6-20 carbon atoms and an arylalkyl group having 7-20 carbonatoms. At least one of Ar₁ and Ar₂ is halogenated.

In an embodiment, a catalyst composition is provided. The catalystcomposition includes a procatalyst composition and a cocatalyst. Theprocatalyst composition includes an internal electron donor that is ahalogenated amide ester. The halogenated amide ester has the structure(I).

In an embodiment, a process for producing an olefin-based polymer isprovided. The process includes contacting, under polymerizationconditions, an olefin with a catalyst composition. The catalystcomposition includes a halogenated amide ester of structure (I). Theprocess further includes forming an olefin-based polymer.

An advantage of the present disclosure is the provision of an improvedprocatalyst composition.

An advantage of the present disclosure is the provision of an improvedcatalyst composition for the polymerization of olefin-based polymers.

An advantage of the present disclosure is the provision of aphthalate-free catalyst composition and a phthalate-free olefin-basedpolymer produced therefrom.

An advantage of the present disclosure is a catalyst composition thatproduces a propylene-based polymer with broad molecular weightdistribution and/or high isotacticity.

An advantage of the present disclosure is a catalyst composition thatproduces a propylene-based polymer with broad molecular weightdistribution in a single reactor.

DETAILED DESCRIPTION

The present disclosure is directed to a halogenated amide ester andprocatalyst/catalyst compositions containing the same and olefin-basedpolymers produced therefrom. The term “halogenated amide ester,” as usedherein is an amide ester having the structure (I):

wherein R₁-R₆ are the same or different. Each of R₁-R₆ is selected fromhydrogen, a halogen, and a hydrocarbyl group having 1-20 carbon atoms.Ar₁ and Ar₂ are the same or different. Each of Ar₁ and Ar₂ is selectedfrom an aryl group having 6-20 carbon atoms and an arylalkyl grouphaving 7-20 carbon atoms. At least one of Ar₁ and Ar₂ is halogenated. Inother words, at least one halogen atom (F, Cl, Br, I) is bonded toeither Ar₁, and/or Ar₂.

Two or more of R₁-R₆ may link to form a mono-cyclic or a poly-cyclicstructure. Ar₁ and/or Ar₂ may be a mono-aromatic or a poly-aromaticstructure. Ar₁ and/or Ar₂ may also include straight, branched, acyclicor cyclic substituents. Nonlimiting examples for Ar₁ and/or Ar₂ includea phenyl group, a naphthyl group, an anthracenyl group, and aphenanthrenyl group.

As used herein, the term “hydrocarbyl” or “hydrocarbon” is a substituentcontaining only hydrogen and carbon atoms, including branched orunbranched, saturated or unsaturated, cyclic, polycyclic, fused, oracyclic species, and combinations thereof. Nonlimiting examples ofhydrocarbyl groups include alkyl-, cycloalkyl-, alkenyl-, alkadienyl-,cycloalkenyl-, cycloalkadienyl-, aryl-, aralkyl, alkylaryl-, andalkynyl-groups.

As used herein, the term “substituted hydrocarbyl” or “substitutedhydrocarbon” is a hydrocarbyl group that is substituted with one or morenonhydrocarbyl substituent groups. A nonlimiting example of anonhydrocarbyl substituent group is a heteroatom. As used herein, a“heteroatom” is an atom other than carbon or hydrogen. The heteroatomcan be a non-carbon atom from Groups IV, V, VI, and VII of the PeriodicTable. Nonlimiting examples of heteroatoms include: halogens (F Cl, Br,I), N, O, P, B, S, and Si. A substituted hydrocarbyl group also includesa halohydrocarbyl group and a silicon-containing hydrocarbyl group. Asused herein, the term “halohydrocarbyl” group is a hydrocarbyl groupthat is substituted with one or more halogen atoms.

In an embodiment, at least one, or at least two, or at least three, ofR₁-R₆ is/are a hydrocarbyl group having 1-20 carbon atoms. In a furtherembodiment, each of R₁ and R₂ is a hydrocarbyl group having 1-20 carbonatoms, or a hydrocarbyl group having 1-6 carbon atoms.

In another embodiment, each of R₃ and R₅ is a hydrocarbyl group having1-20 carbon atoms, or a hydrocarbyl group having 1-6 carbon atoms.

The present disclosure provides a halogenated amide ester. In anembodiment, the halogenated amide ester of structure (I) includes R₁-R₆,each being the same or different. Each of R₁-R₆ is selected fromhydrogen, a halogen, and an acyclic alkyl group having 1-20 carbonatoms, or 1-6 carbon atoms. At least one of, or at least two of R₁-R₆is/are an acyclic alkyl group. The acyclic alkyl group may besubstituted with a member selected from a halogen, a silicon atom, andcombinations thereof.

Ar₁ and Ar₂ are aryl groups and/or arylalkyl groups as discussed abovewith at least one of or each of, Ar₁ and Ar₂ being halogenated.

In an embodiment, the halogenated amide ester has the structure (II):

wherein at least one of R₁₁-R₁₃ and at least one of R₂₁-R₂₃ is a halogenatom.

In an embodiment, each of R₁₂ and R₂₂ of structure (II) is selected fromchlorine and/or fluorine.

In an embodiment, each of R₁₂ and R₂₂ of structure (II) is selected fromchlorine (chlorinated amide ester) and/or fluorine (fluorinated amideester) and at least one of, or at least two of, R₁-R₆ is/are ahydrocarbyl group having 1-20 carbon atoms. In a further embodiment,each of R₁ and R₂ is a hydrocarbyl group having 1-20 carbon atoms, or ahydrocarbyl group having 1-6 carbon atoms.

In an embodiment, each of R₁₂-R₂₂ of structure (II) is selected fromchlorine and/or fluorine. Each of R₃ and R₅ is a hydrocarbyl grouphaving 1-20 carbon atoms, or a hydrocarbyl group having 1-6 carbonatoms.

Nonlimiting examples of fluorinated amide ester include2-((4-fluorobenzamido)methyl)-3-methylbutyl 4-fluorobenzoate,3-((4-fluorobenzamido)methyl)-4-methylpentan-2-yl 4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-5-methylhexan-3-yl 4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-2,5-dimethylhexan-3-yl4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-2,2,5-trimethylhexan-3-yl4-fluorobenzoate, 3-((4-fluorobenzamido)methyl)-2,6-dimethylheptan-4-yl4-fluorobenzoate, 2-((4-fluorobenzamido)methyl)-3-methyl-1-phenylbutyl4-fluorobenzoate, 2-((4-fluorobenzamido)methyl)-4-methylpentyl4-fluorobenzoate, 3-((4-fluorobenzamido)methyl)-5-methylhexan-2-yl4-fluorobenzoate, 4((4-fluorobenzamido)methyl)-6-methylheptan-3-yl4-fluorobenzoate, 4-((4-fluorobenzamido)methyl)-2,6-dimethylheptan-3-yl4-fluorobenzoate,4((4-fluorobenzamido)methyl)-2,2,6-trimethylheptan-3-yl4-fluorobenzoate, 5-((4-fluorobenzamido)methyl)-2,7-dimethyloctan-4-yl4-fluorobenzoate, 24(4-fluorobenzamido)methyl)-4-methyl-1-phenylpentyl4-fluorobenzoate, 2-((4-fluorobenzamido)methyl)-3,3-dimethylbutyl4-fluorobenzoate, 3-((4-fluorobenzamido)methyl)-4,4-dimethylpentan-2-yl4-fluorobenzoate, 4-((4-fluorobenzamido)methyl)-5,5-dimethylhexan-3-yl4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-2,5,5-trimethylhexan-3-yl4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-2,2,5,5-tetramethylhexan-3-yl4-fluorobenzoate,3-((4-fluorobenzamido)methyl)-2,2,6-trimethylheptan-4-yl4-fluorobenzoate,2-((4-fluorobenzamido)methyl)-3,3-dimethyl-1-phenylbutyl4-fluorobenzoate, 3-(4-fluorobenzamido)-2-phenylpropyl 4-fluorobenzoate,4-(4-fluorobenzamido)-3-phenylbutan-2-yl 4-fluorobenzoate,1-(4-fluorobenzamido)-2-phenylpentan-3-yl 4-fluorobenzoate,1-(4-fluorobenzamido)-4-methyl-2-phenylpentan-3-yl 4-fluorobenzoate,1-(4-fluorobenzamido)-4,4-dimethyl-2-phenylpentan-3-yl 4-fluorobenzoate,1-(4-fluorobenzamido)-5-methyl-2-phenylhexan-3-yl 4-fluorobenzoate,3-(4-fluorobenzamido)-1,2-diphenylpropyl 4-fluorobenzoate,3-((4-fluorobenzamido)methyl)-3-isopropyl-5-methylhexan-2-yl4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-4-isopropyl-6-methylheptan-3-yl4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-4-isopropyl-2,6-dimethylheptan-3-yl4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-4-isopropyl-2,2,6-trimethylheptan-3-yl4-fluorobenzoate,5-((4-fluorobenzamido)methyl)-5-isopropyl-2,7-dimethyloctan-4-yl4-fluorobenzoate, 2-((4fluorobenzamido)methyl)-2-isopropyl-4-methyl-1-phenylpentyl4-fluorobenzoate,3-((4-fluorobenzamido)methyl)-3-isopropyl-4-methylpentan-2-yl4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-4-isopropyl-5-methylhexan-3-yl4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-4-isopropyl-2,5-dimethylhexan-3-yl4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-4-isopropyl-2,2,5-trimethylhexan-3-yl4-fluorobenzoate,3-((4-fluorobenzamido)methyl)-3-isopropyl-2,6-dimethylheptan-4-yl4-fluorobenzoate,2-((4-fluorobenzamido)methyl)-2-isopropyl-3-methyl-1-phenylbutyl4-fluorobenzoate,3-((4-fluorobenzamido)methyl)-3-isobutyl-5-methylhexan-2-yl4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-4-isobutyl-6-methylheptan-3-yl4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-4-isobutyl-2,6-dimethylheptan-3-yl4-fluorobenzoate,4-((4-fluorobenzamido)methyl)-4-isobutyl-2,2,6-trimethylheptan-3-yl4-fluorobenzoate,5-((4-fluorobenzamido)methyl)-5-isobutyl-2,7-dimethyloctan-4-yl4-fluorobenzoate, 4-(4-fluorobenzamido)pentan-2-yl 4-fluorobenzonate,and 2-((4-fluorobenzamido)methyl)-2-isobutyl-4-methyl-1-phenylpentyl4-fluorobenzoate.

Nonlimiting examples of chlorinated amide ester include2-((4-chlorobenzamido)methyl)-3-methylbutyl 4-chlorobenzoate,3-((4-chlorobenzamido)methyl)-4-methylpentan-2-yl 4-chlorobenzoate,4((4-chlorobenzamido)methyl)-5-methylhexan-3-yl 4-chlorobenzoate,4((4-chlorobenzamido)methyl)-2,5-dimethylhexan-3-yl 4-chlorobenzoate,

4-((4-chlorobenzamido)methyl)-2,2,5-trimethylhexan-3-yl4-chlorobenzoate, 3-((4-chlorobenzamido)methyl)-2,6-dimethylheptan-4-yl4-chlorobenzoate, 2-((4-chlorobenzamido)methyl)-3-methyl-1-phenylbutyl4-chlorobenzoate, 2-((4-chlorobenzamido)methyl)-4-methylpentyl4-chlorobenzoate, 3-((4-chlorobenzamido)methyl)-5-methylhexan-2-yl4-chlorobenzoate, 4-((4-chlorobenzamido)methyl)-6-methylheptan-3-yl4-chlorobenzoate, 4-((4-chlorobenzamido)methyl)-2,6-dimethylheptan-3-yl4-chlorobenzoate,4-((4-chlorobenzamido)methyl)-2,2,6-trimethylheptan-3-yl4-chlorobenzoate, 5-((4-chlorobenzamido)methyl)-2,7-dimethyloctan-4-yl4-chlorobenzoate, 2-((4-chlorobenzamido)methyl)-4-methyl-1-phenylpentyl4-chlorobenzoate, 2-((4-chlorobenzamido)methyl)-3,3-dimethylbutyl4-chlorobenzoate, 3-((4-chlorobenzamido)methyl)-4,4-dimethylpentan-2-yl4-chlorobenzoate, 4-((4-chlorobenzamido)methyl)-5,5-dimethylhexan-3-yl4-chlorobenzoate,4-((4-chlorobenzamido)methyl)-2,5,5-trimethylhexan-3-yl4-chlorobenzoate,4-((4-chlorobenzamido)methyl)-2,2,5,5-tetramethylhexan-3-yl4-chlorobenzoate,3-((4-chlorobenzamido)methyl)-2,2,6-trimethylheptan-4-yl4-chlorobenzoate,2-((4-chlorobenzamido)methyl)-3,3-dimethyl-1-phenylbutyl4-chlorobenzoate, 3-(4-chloroberizamido)-2-phenylpropyl4-chlorobenzoate, 4-(4-chlorobenzamido)-3-phenylbutan-2-yl4-chlorobenzoate, 1-(4-chlorobenzamido)-2-phenylpentan-3-yl4-chlorobenzoate, 1-(4-chlorobenzamido)-4-methyl-2-phenylpentan-3-yl4-chlorobenzoate, 1-(4-chlorobenzamido)-4,4-dimethyl-2-phenylpentan-3-yl4-chlorobenzoate, 1-(4-chlorobenzamido)-5-methyl-2-phenylhexan-3-yl4-chlorobenzoate, 3-(4-chlorobenzamido)-1,2-diphenylpropyl4-chlorobenzoate,3-((4-chlorobenzamido)methyl)-3-isopropyl-5-methylhexan-2-yl4-chlorobenzoate,4-((4-chlorobenzamido)methyl)-4-isopropyl-6-methylheptan-3-yl4-chlorobenzoate,4-((4-chlorobenzamido)methyl)-4-isopropyl-2,6-dimethylheptan-3-yl4-chlorobenzoate,4-((4-chlorobenzamido)methyl)-4-isopropyl-2,2,6-trimethylheptan-3-yl4-chlorobenzoate,5-((4-chlorobenzamido)methyl)-5-isopropyl-2,7-dimethyloctan-4-yl4-chlorobenzoate, 2-((4chlorobenzamido)methyl)-2-isopropyl-4-methyl-1-phenylpentyl4-chlorobenzoate,3-((4-chlorobenzamido)methyl)-3-isopropyl-4-methylpentan-2-yl4-chlorobenzoate,4-((4-chlorobenzamido)methyl)-4-isopropyl-5-methylhexan-3-yl4-chlorobenzoate,4-((4-chlorobenzamido)methyl)-4-isopropyl-2,5-dimethylhexan-3-yl4-chlorobenzoate,4-((4-chlorobenzamido)methyl)-4-isopropyl-2,2,5-trimethylhexan-3-yl4-chlorobenzoate,3-((4-chlorobenzamido)methyl)-3-isopropyl-2,6-dimethylheptan-4-yl4-chlorobenzoate,2-((4-chlorobenzamido)methyl)-2-isopropyl-3-methyl-1-phenylbutyl4-chlorobenzoate,3-((4-chlorobenzamido)methyl)-3-isobutyl-5-methylhexan-2-yl4-chlorobenzoate,4-((4-chlorobenzamido)methyl)-4-isobutyl-6-methylheptan-3-yl4-chlorobenzoate,4-((4-chlorobenzamido)methyl)-4-isobutyl-2,6-dimethylheptan-3-yl4-chlorobenzoate,4-((4-chlorobenzamido)methyl)-4-isobutyl-2,2,6-trimethylheptan-3-yl4-chlorobenzoate,5-((4-chlorobenzamido)methyl)-5-isobutyl-2,7-dimethyloctan-4-yl4-chlorobenzoate, 4-(4-chlororoobenzamido)pentan-2-yl 4-chlorobenzonate,and 2-((4-chlorobenzamido)methyl)-2-isobutyl-4-methyl-1-phenylpentyl4-chlorobenzoate.

In an embodiment, each of R₁₂ and R₂₂ of structure (II) is fluorine andeach of R₃ and R₅ is a methyl group.

In an embodiment, each of R₁₂ and R₂₂ of structure (II) is fluorine andeach of R₁ and R₂ is a methyl group.

In an embodiment, each of R₁₂ and R₂₂ of structure (II) is fluorine andeach of R₁ and R₂ is an isopropyl group.

In an embodiment, each of R₁₂ and R₂₂ of structure (II) is fluorine andeach of R₁ and R₂ is an isobutyl group.

In an embodiment, each of R₁₂ and R₂₂ of structure (II) is fluorine, R₁is an isopropyl group, and R₂ is an isobutyl group.

In an embodiment, each of R₁₂ and R₂₂ of structure (II) is chlorine andeach of R₃ and R₅ is a methyl group.

In an embodiment, each of R₁₂ and R₂₂ is chlorine and each of R₁ and R₂is a methyl group.

In an embodiment, each of R₁₂ and R₂₂ is chlorine and each of R₁ and R₂is an isopropyl group.

In an embodiment, each of R₁₂ and R₂₂ is chlorine and each of R₁ and R₂is an isobutyl group.

In an embodiment, each of R₁₂ and R₂₂ of structure (II) is chlorine, R₁is an isopropyl group, and R₂ is an isobutyl group.

The present halogenated amide ester may comprise two or more embodimentsenclosed herein.

In an embodiment, a procatalyst composition is provided. The procatalystcomposition includes a combination of a magnesium moiety, a titaniummoiety and an internal electron donor. In other words, the procatalystcomposition is a reaction product of a procatalyst precursor, ahalogenated amide ester, an optional halogenting agent, and an optionaltitanating agent. The internal electron donor includes a halogenatedamide ester of structure (I):

wherein R₁-R₆ are the same or different. Each of R₁-R₆ is selected fromhydrogen, a halogen, and a substituted/unsubstituted hydrocarbyl grouphaving 1-20 atoms. Ar₁ and Ar₂ are the same or different. Each of Ar₁and Ar₂ is selected from an aryl group having 6-20 atoms and anarylalkyl group having 7-20 carbon atoms. At least one of Ar₁ and Ar₂ ishalogenated.

Two or more of the R₁-R₆ may link to form a cyclic or poly-cyclicstructure as previously discussed. Ar₁ and Ar₂ may be any compound orstructure as previously discussed. The internal electron donor may beany of the foregoing halogenated amide esters.

The procatalyst composition is produced by halogenating/titanating aprocatalyst precursor in the presence of the internal electron donor. Asused herein, an “internal electron donor” is a compound added orotherwise formed during formation of the procatalyst composition thatdonates at least one pair of electrons to one or more metals present inthe resultant procatalyst composition. The internal electron donor isthe halogenated amide ester. Not wishing to be bound by any particulartheory, it is believed that during halogenation and titanation theinternal electron donor (1) regulates the formation of active sites, (2)regulates the position of titanium on the magnesium-based support andthereby enhances catalyst stereoselectivity, (3) facilitates conversionof the magnesium and titanium moieties into respective halides and (4)regulates the crystallite size of the magnesium halide support duringconversion. Thus, provision of the internal electron donor yields aprocatalyst composition with enhanced stereoselectivity.

The procatalyst precursor may be a magnesium moiety compound (MagMo), amagnesium mixed metal compound (MagMix), or a benzoate-containingmagnesium chloride compound (BenMag). In an embodiment, the procatalystprecursor is a magnesium moiety (“MagMo”) precursor. The “MagMoprecursor” contains magnesium as the sole metal component. The MagMoprecursor includes a magnesium moiety. Nonlimiting examples of suitablemagnesium moieties include anhydrous magnesium chloride and/or itsalcohol adduct, magnesium alkoxide or aryloxide, mixed magnesium alkoxyhalide, and/or carbonated magnesium dialkoxide or aryloxide. In oneembodiment, the MagMo precursor is a magnesium di-(C₁₋₄)alkoxide. In afurther embodiment, the MagMo precursor is diethoxymagnesium.

The MagMix includes magnesium and at least one other metal atom. Theother metal atom can be a main group metal or a transition metal, or atransition metal of IIIB-VIIIB element. In an embodiment, the transitionmetal is selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, and Hf.In a further embodiment, the MagMix precursor is a mixedmagnesium/titanium compound (“MagTi”). The “MagTi precursor” has theformula Mg_(d)Ti(OR^(e))_(f)X_(g) wherein R^(e) is an aliphatic oraromatic hydrocarbon radical having 1 to 14 carbon atoms or COR′ whereinR′ is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbonatoms; each OR^(e) group is the same or different; X is independentlychlorine, bromine or iodine, preferably chlorine; d is 0.5 to 56, or 2to 4; f is 2 to 116 or 5 to 15; and g is 0.5 to 116, or 1 to 3.

In an embodiment, the procatalyst precursor is a benzoate-containingmagnesium chloride material. As used herein, a “benzoate-containingmagnesium chloride” (“BenMag”) is a magnesium chloride procatalyst(i.e., a halogenated procatalyst precursor) containing a benzoateinternal electron donor. The BenMag material may also include a titaniummoiety, such as a titanium halide. The benzoate internal donor is labileand can be replaced by other electron donors during procatalystsynthesis. Nonlimiting examples of suitable benzoate groups includeethyl benzoate, methyl benzoate, ethyl p-methoxybenzoate, methylp-ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl p-chlorobenzoate. In oneembodiment, the benzoate group is ethyl benzoate. Nonlimiting examplesof suitable BenMag procatalyst precursors include catalysts of the tradenames SHAC™ 103 and SHAC™ 310 available from The Dow Chemical Company,Midland, Mich.

In an embodiment, the BenMag procatalyst precursor is a product ofhalogenation of any procatalyst precursor (i.e., a MagMo precursor or aMagTi precursor) in the presence of a benzoate compound with thestructure (IV)

wherein R₁-R₅ are H, a C₁-C₂₀ hydrocarbyl group which may containheteroatoms including F, Cl, Br, I, O, S, N, P, and Si, and R′ is aC₁-C₂₀ hydrocarbyl group which may optionally contain heteroatom(s)including F, Cl, Br, I, O, S, N, P, and Si. Preferably, R₁-R₅ areselected from H and a C₁-C₂₀ alkyl group and R′ is selected from aC₁-C₂₀ alkyl group and an alkoxyalkyl group.

Halogenation/titanation of the procatalyst precursor in the presence ofthe internal electron donor produces a procatalyst composition whichincludes a combination of a magnesium moiety, a titantium moiety, andthe internal electron donor (a halogenated amide ester). In anembodiment, the magnesium and titanium moieties are respective halides,such as magnesium chloride and titanium chloride. Bounded by noparticular theory, it is believed that the magnesium halide is a supportupon which the titanium halide is deposited and onto which the internalelectron donor is incorporated.

The resulting procatalyst composition has a titanium content of fromabout 1.0 percent by weight to about 6.0 percent by weight, based on thetotal solids weight, or from about 1.5 percent by weight to about 5.5percent by weight, or from about 2.0 percent by weight to about 5.0percent by weight. The weight ratio of titanium to magnesium in thesolid procatalyst composition is suitably between about 1:3 and about1:160, or between about 1:4 and about 1:50, or between about 1:6 and1:30. The internal electron donor is present in an amount from about 0.1wt % to about 20.0 wt %, or from about 1.0 wt % to about 15 wt %. Theinternal electron donor may be present in the procatalyst composition ina molar ratio of internal electron donor to magnesium of from about0.005:1 to about 1:1, or from about 0.01:1 to about 0.4:1. Weightpercent is based on the total weight of the procatalyst composition.

Ethoxide content in the procatalyst composition indicates thecompleteness of conversion of precursor metal ethoxide into a metalhalide. The halogenated amide ester assists in converting ethoxide intohalide during halogenation. In an embodiment, the procatalystcomposition includes from about 0.01 wt % to about 1.0 wt %, or fromabout 0.05 wt % to about 0.5 wt % ethoxide. Weight percent is based onthe total weight of the procatalyst composition.

In an embodiment, the internal electron donor is a mixed internalelectron donor. As used herein, a “mixed internal electron donor” is (i)a halogenated amide ester, (ii) an electron donor component that donatesa pair of electrons to one or more metals present in the resultantprocatalyst composition, and (iii) optionally other components. In anembodiment, the electron donor component is a benzoate, such as ethylbenzoate and/or methoxypropan-2-yl benzoate. The procatalyst compositionwith the mixed internal electron donor can be produced by way of theprocatalyst production procedure as previously disclosed.

In an embodiment, the internal electron donor and/or the mixed internalelectron donor are/is phthalate-free.

In an embodiment, the procatalyst composition is phthalate-free.

The present procatalyst composition may comprise two or more embodimentsdisclosed herein.

In an embodiment, a catalyst composition is provided. As used herein, “acatalyst composition” is a composition that forms an olefin-basedpolymer when contacted with an olefin under polymerization conditions.The catalyst composition includes a procatalyst composition and acocatalyst. The procatalyst composition can be any of the foregoingprocatalyst compositions with an internal electron donor that is ahalogenated amide ester of structure (I) or structure (II) as disclosedherein. The catalyst composition may optionally include an externalelectron donor and/or an activity limiting agent.

In an embodiment, the internal electron donor of the catalystcomposition is a mixed internal electron donor as disclosed above.

The catalyst composition includes a cocatalyst. As used herein, a“cocatalyst” is a substance capable of converting the procatalyst to anactive polymerization catalyst. The cocatalyst may include hydrides,alkyls, or aryls of aluminum, lithium, zinc, tin, cadmium, beryllium,magnesium, and combinations thereof. In an embodiment, the cocatalyst isa hydrocarbyl aluminum compound represented by the formulaR_(n)AlX_(3-n) wherein n=1 2, or 3, R is an alkyl, and X is a halide oralkoxide. Nonlimiting examples of suitable cocatalyst includetrimethylaluminum, triethylaluminum, triisobutylaluminum, andtri-n-hexylaluminum.

In an embodiment, the cocatalyst is triethylaluminum. The molar ratio ofaluminum to titanium is from about 5:1 to about 500:1, or from about10:1 to about 200:1, or from about 15:1 to about 150:1, or from about20:1 to about 100:1, or from about 30:1 to about 60:1. In anotherembodiment, the molar ratio of aluminum to titanium is about 35:1.

In an embodiment, the present catalyst composition includes an externalelectron donor. As used herein, an “external electron donor” (or “EED”)is a compound added independent of procatalyst formation and includes atleast one functional group that is capable of donating a pair ofelectrons to a metal atom. A “mixed external electron donor” (or “MEED”)is a mixture of two or more external electron donors. Bounded by noparticular theory, it is believed that provision of one or more externalelectron donors in the catalyst composition effects the followingproperties of the formant polymer: level of tacticity (i.e., xylenesoluble material), molecular weight (i.e., melt flow), molecular weightdistribution (MWD), melting point, and/or oligomer level.

In an embodiment, the external electron donor may be selected from oneor more of the following: a silicon compound, a bidentate compound, anamine, an ether, a carboxylate, a ketone, an amide, a carbamate, aphosphine, a phosphate, a phosphite, a sulfonate, a sulfone, asulfoxide, and any combination of the foregoing.

In an embodiment, the EED is a silicon compound having the generalformula (III):SiR_(m)(OR′)_(4-m)   (III)wherein R independently each occurrence is hydrogen or a hydrocarbyl oran amino group, optionally substituted with one or more substituentscontaining one or more Group 14, 15, 16, or 17 heteroatoms. R containsup to 20 atoms not counting hydrogen and halogen. R′ is a C₁₋₂₀ alkylgroup, and m is 0, 1, or 2. In an embodiment, R is C₆₋₁₂ aryl, alkylarylor aralkyl, C₃₋₁₂ cycloalkyl, C₁₋₂₀ linear alkyl or alkenyl, C₃₋₁₂branched alkyl, or C₂₋₁₂ cyclic amino group, R′ is C₁₋₄ alkyl, and m is1 or 2.

Nonlimiting examples of suitable silicon compounds for the EED includedialkoxysilanes, trialkoxysilanes, and tetraalkoxysilanes such asdicyclopentyldimethoxysilane, diisopropyldimethoxysilane (DCPDMS),bis(perhydroisoquinolino)dimethoxysilane,methylcyclohexyldimethoxysilane, tetraethoxysilane,n-propyltrimethoxysilane, n-propyltriethoxysilane,diethylaminotriethoxysilane, bis(trimethylsilylmethyl)dimethoxysilane,and any combination thereof.

In an embodiment, the EED is a bidentate compound. A “bidentatecompound” is a molecule or compound that contains at least twooxygen-containing functional groups separated by a C₂-C₁₀ hydrocarbonchain, the oxygen-containing functional groups being the same ordifferent and at least one oxygen-containing functional group being anether group or a carboxylate group, the bidentate composition excludingphthalates. Nonlimiting examples of suitable oxygen-containingfunctional groups for the bidentate composition include carboxylate,carbonate, ketone, ether, carbamate, amide, sulfoxide, sulfone,sulfonate, phosphite, phosphinate, phosphate, phosphonate, and phosphineoxide. One or more carbon atoms in the C₂-C₁₀ chain may be substitutedwith heteroatoms from Group 14, 15, and 16. One or more H atoms in theC₂-C₁₀ chain may be substituted with alkyl, cycloalkyl, alkenyl,cycloalkenyl, aryl, alkylaryl, aralkyl, halogen, or functional groupscontaining a heteroatom from Group 14, 15, or 16. Nonlimiting examplesof suitable bidentate compounds include diethers, succinates,dialkoxybenzenes, alkoxy ester, and/or diol esters.

In an embodiment, the bidentate compound is a diether such as3,3-bis(methoxymethyl)-2,5-dimethylhexane,4,4-bis(methoxymethyl)-2,6-dimethylheptane, and9,9-bis(methoxymethyl)fluorene.

In an embodiment, the bidentate compound is a diol ester such as2,4-pentanediol di(benzoate), 2,4-pentanediol di(2-methylbenzoate),2,4-pentanediol di(4-n-butylbenzoate), 2,2,4-trimethyl-1,3-pentanedioldiisobutyrate and/or 2,2,4-trimethyl-1,3-pentanediol dibenzoate.

In an embodiment, the carboxylate is a benzoate such as ethyl benzoateand ethyl 4-ethoxybenzoate.

In an embodiment the external electron donor is a phosphite such astrimetyl phosphate, triethyl phosphate, and/or tri-n-propyl phosphite.

In an embodiment, the external electron donor is an alkoxy ester such asmethyl 1-methoxybicylco[2.2.1]-hept-5-ene-2-carboxylate, methyl3-methoxypropionate, methyl 3-methoxy-2-methylpropanoate, and/or ethyl3-methoxy-2-methylpropanoate.

In an embodiment, the external electron donor is a succinate such asdiethyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate,and/or diethyl 2,3-diisobutylsuccinate.

In an embodiment, the external electron donor is a dialkoxybenzene suchas 1,2-diethoxybenzene, 1,2-di-n-butoxybenzene, and/or1-ethoxy-2-n-pentoxybenzene.

In an embodiment, the external electron donor is an amine such as2,2,6,6-tetramethylpiperidine.

It is further understood that the EED may be a MEED which may comprisetwo or more of any of the foregoing EED compounds.

In an embodiment, the catalyst composition includes an activity limitingagent (ALA). As used herein, an “activity limiting agent” (“ALA”) is amaterial that reduces catalyst activity at elevated temperature (i.e.,temperature greater than about 85° C.). An ALA inhibits or otherwiseprevents polymerization reactor upset and ensures continuity of thepolymerization process. Typically, the activity of Ziegler-Nattacatalysts increases as the reactor temperature rises. Ziegler-Nattacatalysts also typically maintain high activity near the softening pointtemperature of the polymer produced. The heat generated by theexothermic polymerization reaction may cause polymer particles to formagglomerates and may ultimately lead to disruption of continuity for thepolymer production process. The ALA reduces catalyst activity atelevated temperature, thereby preventing reactor upset, reducing (orpreventing) particle agglomeration, and ensuring continuity of thepolymerization process.

The ALA may or may not be a component of the EED and/or the MEED. Theactivity limiting agent may be a carboxylic acid ester, a diether, apoly(alkene glycol), a succinate, a diol ester, and combinationsthereof. The carboxylic acid ester can be an aliphatic or aromatic,mono-or poly-carboxylic acid ester. Nonlimiting examples of suitablecarboxylic acid esters include benzoates, C₁₋₄₀ alkyl esters ofaliphatic C₂₋₄₀ mono-/di-carboxylic acids, C₂₋₄₀ mono-/poly-carboxylatederivatives of C₂₋₁₀₀ (poly)glycols, C₂₋₁₀₀ (poly)glycol ethers, and anycombination thereof. Further nonlimiting examples of carboxylic acidesters include laurates, myristates, palmitates, stearates, oleates, andsebacates, and mixtures thereof. In a further embodiment, the ALA isethyl 4-ethoxybenzoate or isopropyl myristate or di-n-butyl sebacate.

The catalyst composition may include any of the foregoing externalelectron donors in combination with any of the foregoing activitylimiting agents. The external electron donor and/or activity limitingagent can be added into the reactor separately. Alternatively, theexternal electron donor and the activity limiting agent can be mixedtogether in advance and then added to the catalyst composition and/orinto the reactor as a mixture. In the mixture, more than one externalelectron donor or more than one activity limiting agent can be used.Nonlimiting examples of suitable EED/ALA mixtures includedicyclopentyldimethoxysilane and isopropyl myristate,dicyclopentyldimethoxysilane and poly(ethylene glycol) laurate,diisopropyldimethoxysilane and isopropyl myristate,methylcyclohexyldimethoxysilane and isopropyl myristate,methylcyclohexyldimethoxysilane and ethyl 4-ethoxybenzoate,n-propyltrimethoxysilane and isopropyl myristate,dimethyldimethoxysilane and methylcyclohexyldimethoxysilane andisopropyl myristate, dicyclopentyldimethoxysilane and tetraethoxysilaneand isopropyl myristate, dicyclopentyldimethoxysilane andtetraethoxysilane and ethyl 4-ethoxybenzoate,dicyclopentyldimethoxysilane and n-propyltriethoxysilane and isopropylmyristate, diisopropyldimethoxysilane and n-propyltriethoxysilane andisopropyl myristate, dicyclopentyldimethoxysilane and isopropylmyristate and poly(ethylene glycol)dioleate,dicyclopentyldimethoxysilane and diisopropyldimethoxysilane andn-propyltriethoxysilane and isopropyl myristate, and combinationsthereof.

The present catalyst composition may comprise two or more embodimentsdisclosed herein.

In an embodiment, a process for producing an olefin-based polymer isprovided. The process includes contacting an olefin with a catalystcomposition under polymerization conditions. The catalyst compositionincludes a halogenated amide ester. The halogenated amide ester can beany halogenated amide ester as disclosed herein. The process furtherincludes forming an olefin-based polymer.

The catalyst composition includes a procatalyst composition and acocatalyst. The procatalyst composition is any procatalyst compositiondisclosed herein and includes a halogenated amide ester of structure (I)or structure (II) as the internal electron donor. The cocatalyst may beany cocatalyst as disclosed herein. The catalyst composition mayoptionally include an external electron donor and/or an activitylimiting agent as previously disclosed.

The olefin-based polymer contains halogenated amide ester correspondingto the internal electron donor of structure (I) or structure (II)present in the procatalyst composition. In an embodiment, theolefin-based polymer can be a propylene-based olefin, an ethylene-basedolefin, and combinations thereof. In an embodiment, the olefin-basedpolymer is a propylene-based polymer.

One or more olefin monomers can be introduced into a polymerizationreactor to react with the catalyst and to form a polymer, or a fluidizedbed of polymer particles. Nonlimiting examples of suitable olefinmonomers include ethylene, propylene, C₄₋₂₀ α-olefins, such as 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene,1-dodecene and the like.

As used herein, “polymerization conditions” are temperature and pressureparameters within a polymerization reactor suitable for promotingpolymerization between the catalyst composition and an olefin to formthe desired polymer. The polymerization process may be a gas phase, aslurry, or a bulk polymerization process, operating in one, or more thanone, polymerization reactor. Accordingly, the polymerization reactor maybe a gas phase polymerization reactor, a liquid-phase polymerizationreactor, or a combination thereof.

It is understood that provision of hydrogen in the polymerizationreactor is a component of the polymerization conditions. Duringpolymerization, hydrogen is a chain transfer agent and affects themolecular weight (and correspondingly the melt flow rate) of theresultant polymer. The polymerization process may include apre-polymerization step and/or a pre-activation step.

In an embodiment, the process includes mixing the external electrondonor (and optionally the activity limiting agent) with the procatalystcomposition. The external electron donor and/or the activity limitingagent can be complexed with the cocatalyst and mixed with theprocatalyst composition (pre-mix) prior to contact between the catalystcomposition and the olefin. In another embodiment, the external electrondonor and/or the activity limiting agent can be added independently tothe polymerization reactor.

In an embodiment, the olefin is propylene and optionally ethylene and/or1-butene. The process includes forming a propylene-based polymer(propylene homopolymer or propylene copolymer) having one or more of thefollowing properties:

-   -   a melt flow rate (MFR) from about 0.01 g/10 min to about 800        g/10 min, or from about 0.1 g/10 min to about 200 g/10 min, or        from about 0.5 g/10 min to about 150 g/10 min, or from about 1        g/10 min to about 70 g/10 min;    -   a xylene solubles content from about 0.5% to about 10%, or from        about 1% to about 8%, or from about 1% to about 4%;    -   a polydispersity index (PDI) from about 5.0 to about 20.0, or        from about 6.0 to about 15, or from about 6.5 to about 10, or        from about 7.0 to about 9.0;    -   when a comonomer is present it is present in an amount form        about 0.001 wt % to abut 20 wt %, or from about 0.01 wt % to        about 15 wt %, or from about 0.1 wt % to about 10 wt % (based on        total weight of the polymer); and/or    -   internal electron donor (halogenated amide ester) or mixed        internal electron donor (halogenated amide ester and a benzoate)        present from about 1 ppb to about 50 ppm, or from about 10 ppb        to about 25 ppm, or from about 100 ppb to about 10 ppm.

The present disclosure provides another process for producing anolefin-based polymer. In an embodiment, a process for producing anolefin-based polymer is provided which includes contacting propylenewith a catalyst composition comprising a halogenated amide ester to forma propylene-based polymer. The contact between the propylene and thecatalyst composition occurs in a first polymerization reactor underpolymerization conditions. The process further includes contactingethylene and optionally at least one other olefin in the presence of thepropylene-based polymer. The contact between the ethylene, theolefin(s), and the propylene-based polymer occurs in a secondpolymerization reactor under polymerization conditions and forms apropylene impact copolymer.

In an embodiment, the first reactor and the second reactor operate inseries whereby the effluent of the first reactor (i.e., thepropylene-based polymer) is charged to the second reactor. Additionalolefin monomer is added to the second polymerization reactor to continuepolymerization. Additional catalyst composition (and/or any combinationof individual catalyst components—i.e., procatalyst, cocatalyst, EED,ALA) may be added to the second polymerization reactor. The additionalcatalyst composition/components added to the second reactor may be thesame or different than the catalyst composition/components introduced inthe first reactor.

In an embodiment, the propylene-based polymer produced in the firstreactor is a propylene homopolymer. The propylene homopolymer is chargedto the second reactor where ethylene and propylene are contacted witheach other in the presence of the propylene homopolymer. This forms apropylene impact copolymer having a propylene homopolymer continuous (ormatrix) phase and a discontinuous phase (or rubber phase) selected froma propylene-based copolymer (i.e., a propylene/ethylene copolymer) or anethylene-based copolymer (i.e., an ethylene/propylene copolymer). Thediscontinuous phase is dispersed in the continuous phase.

The propylene impact copolymer may have an Fc value from about 1 wt % toabout 50 wt %, or from about 10 wt % to about 40 wt %, or from about 20wt % to about 30 wt %. As used herein, “fraction copolymer” (“Fc”) isthe weight percent of the discontinuous phase present in theheterophasic copolymer. The Fc value is based on the total weight of thepropylene impact copolymer.

The propylene impact copolymer may have an Ec value from about 1 wt % toabout 100 wt %, or from about 20 wt % to about 90 wt %, or from about 30wt % to about 80 wt %, or from about 40 wt % about 60 wt %. As usedherein, “ethylene content” (“Ec”) is the weight percent of ethylenepresent in the discontinuous phase of the propylene impact copolymer.The Ec value is based on the total weight of the discontinuous (orrubber) phase.

The present processes for production olefin-based polymer may comprisetwo or more embodiments disclosed herein.

Definitions

All references to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2003. Also, any references to a Group or Groups shall be tothe Groups or Groups reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. Unless stated to thecontrary, implicit from the context, or customary in the art, all partsand percents are based on weight. For purposes of United States patentpractice, the contents of any patent, patent application, or publicationreferenced herein are hereby incorporated by reference in their entirety(or the equivalent US version thereof is so incorporated by reference),especially with respect to the disclosure of synthetic techniques,definitions (to the extent not inconsistent with any definitionsprovided herein) and general knowledge in the art.

Any numerical range recited herein, includes all values from the lowervalue to the upper value, in increments of one unit, provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent, or a value of a compositional or a physical property, suchas, for example, amount of a blend component, softening temperature,melt index, etc., is between 1 and 100, it is intended that allindividual values, such as, 1, 2, 3, etc., and all subranges, such as, 1to 20, 55 to 70, 197 to 100, etc., are expressly enumerated in thisspecification. For values which are less than one, one unit isconsidered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. These areonly examples of what is specifically intended, and all possiblecombinations of numerical values between the lowest value and thehighest value enumerated, are to be considered to be expressly stated inthis application. In other words, any numerical range recited hereinincludes any value or subrange within the stated range. Numerical rangeshave been recited, as discussed herein, reference melt index, melt flowrate, and other properties.

The term “alkyl,” as used herein, refers to a branched or unbranched,saturated or unsaturated acyclic hydrocarbon radical. Nonlimitingexamples of suitable alkyl radicals include, for example, methyl, ethyl,n-propyl, i-propyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl), etc.The alkyls have 1 to 20 carbon atoms.

The term “aryl” or “aryl group,” as used herein, is a substituentderived from an aromatic hydrocarbon compound. An aryl group has a totalof from six to twenty ring atoms, and has one or more rings which areseparate or fused, and may be substituted with alkyl and/or halo groups.The aromatic ring(s) may include phenyl, naphthyl, anthracenyl, andbiphenyl, among others.

The term “arylalkyl” or “arylalkyl group,” as used herein, is a compoundcontaining both aliphatic and aromatic structures. The term “arylalkylgroup” includes “aralkyl groups” (an alkyl group substituted by at leastone aryl group) and/or “alkylaryl groups” (an aryl group substituted byat least one alkyl group).

The terms “blend” or “polymer blend,” as used herein, is a blend of twoor more polymers. Such a blend may or may not be miscible (not phaseseparated at molecular level). Such a blend may or may not be phaseseparated. Such a blend may or may not contain one or more domainconfigurations, as determined from transmission electron spectroscopy,light scattering, x-ray scattering, and other methods known in the art.

The term “composition,” as used herein, includes a mixture of materialswhich comprise the composition, as well as reaction products anddecomposition products formed from the materials of the composition.

The term “comprising,” and derivatives thereof, is not intended toexclude the presence of any additional component, step or procedure,whether or not the same is disclosed herein. In order to avoid anydoubt, all compositions claimed herein through use of the term“comprising” may include any additional additive, adjuvant, or compoundwhether polymeric or otherwise, unless stated to the contrary. Incontrast, the term, “consisting essentially of” excludes from the scopeof any succeeding recitation any other component, step or procedure,excepting those that are not essential to operability. The term“consisting of” excludes any component, step or procedure notspecifically delineated or listed. The term “or”, unless statedotherwise, refers to the listed members individually as well as in anycombination.

The term, “ethylene-based polymer,” as used herein, is a polymer thatcomprises a majority weight percent polymerized ethylene monomer (basedon the total weight of polymerizable monomers), and optionally maycomprise at least one polymerized comonomer.

The term “olefin-based polymer” is a polymer containing, in polymerizedform, a majority weight percent of an olefin, for example ethylene orpropylene, based on the total weight of the polymer. Nonlimitingexamples of olefin-based polymers include ethylene-based polymers andpropylene-based polymers.

The term “polymer” is a macromolecular compound prepared by polymerizingmonomers of the same or different type. “Polymer” includes homopolymers,copolymers, terpolymers, interpolymers, and so on. The term“interpolymer” is a polymer prepared by the polymerization of at leasttwo types of monomers or comonomers. It includes, but is not limited to,copolymers (which usually refers to polymers prepared from two differenttypes of monomers or comonomers, terpolymers (which usually refers topolymers prepared from three different types of monomers or comonomers),tetrapolymers (which usually refers to polymers prepared from fourdifferent types of monomers or comonomers), and the like.

The term, “propylene-based polymer,” as used herein, is a polymer thatcomprises a majority weight percent polymerized propylene monomer (basedon the total amount of polymerizable monomers), and optionally maycomprise at least one polymerized comonomer.

The term “substituted alkyl,” as used herein, is an alkyl as previouslydefined described in which one or more hydrogen atom bound to any carbonof the alkyl is replaced by another group such as a halogen, aryl,substituted aryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl,substituted heterocycloalkyl, haloalkyl, hydroxy, amino, phosphido,alkoxy, amino, thio, nitro, silyl, and combinations thereof. Suitablesubstituted alkyls include, for example, benzyl, trifluoromethyl and thelike.

Test Methods

Melt flow rate (MFR) is measured in accordance with ASTM D 1238-01 testmethod at 230° C. with a 2.16 kg weight for propylene-based polymers.

Xylene Solubles (XS) is the weight percent of resin that stays in thesolution after the resin is dissolved in hot xylene and the solution isallowed to cool to 25° C. (Gravimetric XS method according to ASTMD5492-06). XS is measured according to one of the two followingprocedures: (1) Viscotek method: 0.4 g of polymer is dissolved in 20 mlof xylenes with stirring at 130° C. for 30 minutes. The solution is thencooled to 25° C. and after 30 minutes the insoluble polymer fraction isfiltered off. The resulting filtrate is analyzed by Flow InjectionPolymer Analysis using a Viscotek ViscoGEL H-100-3078 column with THFmobile phase flowing at 1.0 ml/min. The column is coupled to a ViscotekModel 302 Triple Detector Array, with light scattering, viscometer andrefractometer detectors operating at 45° C. Instrument calibration wasmaintained with Viscotek PoIyCAL™ polystyrene standards. (2) NMR method:XS is measured using a ¹H NMR method as described in U.S. Pat. No.5,539,309, the entire content of which is incorporated herein byreference. Both of the methods are calibrated against the gravimetricASTM method.

Polydispersity Index (PDI) is measured by an AR-G2 rheometer which is astress control dynamic spectrometer manufactured by TA Instruments usinga method according to Zeichner G R, Patel P D (1981) “A comprehensiveStudy of Polypropylene Melt Rheology”, Proc. of the 2^(nd) WorldCongress of Chemical Eng., Montreal, Canada. An ETC oven is used tocontrol the temperature at 180° C.±0.1° C. Nitrogen is used to purge theinside the oven to keep the sample from degradation by oxygen andmoisture. A pair of 25 mm in diameter cone and plate sample holder isused. Samples are compress molded into 50 mm×100 mm×2 mm plaque. Samplesare then cut into 19 mm square and loaded on the center of the bottomplate. The geometries of upper cone is (1) Cone angle: 5:42:20(deg:min:sec); (2) Diameter: 25 mm; (3) Truncation gap: 149 micron. Thegeometry of the bottom plate is 25 mm cylinder.

Testing procedure:

-   -   (1) The cone & plate sample holder is heated in the ETC oven at        180° C. for 2 hours. Then the gap is zeroed under blanket of        nitrogen gas.    -   (2) Cone is raised to 2.5 mm and sample loaded unto the top of        the bottom plate.    -   (3) Start timing for 2 minutes.    -   (4) The upper cone is immediately lowered to slightly rest on        top of the sample by observing the normal force.    -   (5) After two minutes the sample is squeezed down to 165 micron        gap by lower the upper cone.    -   (6) The normal force is observed. When the normal force is down        to <0.05 Newton the excess sample is removed from the edge of        the cone and plate sample holder by a spatula.    -   (7) The upper cone is lowered again to the truncation gap which        is 149 micron.    -   (8) An Oscillatory Frequency Sweep test is performed under these        conditions:        -   (i) Test delayed at 180° C. for 5 minutes.        -   (ii) Frequencies: 628.3 r/s to 0.1 r/s.        -   (iii) Data acquisition rate: 5 point/decade.        -   (iv) Strain: 10%    -   (9) When the test is completed the crossover modulus (Gc) is        detected by the Rheology Advantage Data Analysis program        furnished by TA Instruments.    -   (10) PDI=100,000÷Gc (in Pa units).

Final melting point (T_(MF)) is the temperature to melt the most perfectcrystal in the sample and is a measure for isotacticity and inherentpolymer crystallizability. The test is conducted using a TA Q100Differential Scanning calorimeter. A sample is heated from 0° C. to 240°C. at a rate of 80° C./min, cooled at the same rate to 0° C., thenheated again at the same rate up to 150° C., held at 150° C. for 5minutes and the heated from 150° C. to 180° C. at 1.25° C./min. TheT_(MF) is determined from this last cycle by calculating the onset ofthe baseline at the end of the heating curve.

Testing procedure:

-   -   (1) Calibrate instrument with high purity indium as standard.    -   (2) Purge the instrument head/cell with a constant 50 ml/min        flow rate of nitrogen constantly.    -   (3) Sample preparation:        -   Compression mold 1.5 g of powder sample using a            30-G302H-18-CX Wabash Compression Molder (30 ton): (a) heat            mixture at 230° C. for 2 minutes at contact; (b) compress            the sample at the same temperature with 20 ton pressure for            1 minute; (c) cool the sample to 45° F. and hold for 2            minutes with 20 ton pressure; (d) cut the plaque into 4 of            about the same size, stack them together, and repeat steps            (a)-(c) in order to homogenize sample.    -   (4) Weigh a piece of sample (preferably between 5 to 8 mg) from        the sample plaque and seal it in a standard aluminum sample pan.        Place the sealed pan containing the sample on the sample side of        the instrument head/cell and place an empty sealed pan in the        reference side. If using the auto sampler, weigh out several        different sample specimens and set up the machine for a        sequence.    -   (5) Measurements:        -   (i) Data storage: off        -   (ii) Ramp 80.00° C./min to 240.00° C.        -   (iii) Isothermal for 1.00 min        -   (iv) Ramp 80.00° C./min to 0.00° C.        -   (v) Isothermal for 1.00 min        -   (vi) Ramp 80.00° C./min to 150.00° C.        -   (vii) Isothermal for 5.00 min        -   (viii) Data storage: on        -   (ix) Ramp 1.25° C./min to 180.00° C.        -   (x) End of method    -   (6) Calculation: T_(MF) is determined by the interception of two        lines. Draw one line from the base-line of high temperature.        Draw another line from through the deflection of the curve close        to the end of the curve at high temperature side.

By way of example and not by limitation, examples of the presentdisclosure will now be provided.

EXAMPLES

1. Synthesis of Halogenated Amide Ester

Ethyl 2-cyano-2-isobutyl-4-methylpentanoate, and ethyl2-cyano-2-isopropyl-3-methylbutyrate

A 500-ml round-bottom flask is fit with magnetic stirrer, and is chargedwith ethyl 2-cyanoacetate (11.3 g, 0.1 mol) and anhydrous DMF (120 ml).To the stirred solution a solution of 1,8-diazabycyclo[5.4.0]undec-7-ene(DBU) (30.4 g, 0.2 mol, 1.0 equiv.) in anhydrous DMF (40 ml) is addeddropwise. After the completion of addition, the mixture is stirred foranother hour. The flask is cooled in an ice-water bath, and a solutionof the iodide (0.2 mol, 1.0 equiv.) in DMF (40 ml) is added dropwise.The mixture is raised to room temperature and stirred for another 14hours until all starting material is converted into the product(monitored by GC). The mixture is poured into ice-water, and extractedwith diethyl ether. The combined ether extract is washed with water andbrine, dried over magnesium sulfate. After filtration, the filtrateconcentrated, and the residue is distilled in vacuo to yield the productas colorless liquid.

Ethyl 2-cyano-2-isopropyl-3-methylbutyrate: Yield 67%; ¹H NMR: δ 4.24(q, 2H, J=7.0 Hz), 2.28 (heptat, 2H, J=7.0 Hz) 1.30 (t, 3H, J=7.0 Hz),1.07 (d, 6H, J=7.0 Hz), 1.01 (d, 6H, J=6.5 Hz).

Ethyl 2-cyano-2-isobutyl-4-methylpentanoate: Yield 88%; ¹H NMR: δ 4.26(q, 2H, J=7.0 Hz), 1.82-1.90 (m, 4H), 1.63-1.70 (m, 2H), 1.34 (t, 3H,J=7.0 Hz), 1.04 (d, 6H, J=6.0 Hz), 0.89 (d, 6H, J=6.0 Hz).

2,2-Disubtituted 3-aminopropanols

A nitrogen purged 1000-ml three-neck round bottom flask is fit withmagnetic stirrer, condenser, and dropping funnel. Powered lithiumaluminum hydride (0.14˜0.18 mol) is added followed by anhydrous THF(140˜180 ml), which can be replaced by commercial 1.0 M lithium aluminumhydride in THF. While stirred, a solution of the ethyl2-cyanocarboxylate compound (0.06˜0.08 mol) in ether (˜200 ml) is addeddropwise to keep the mixture in gentle reflux. Upon the completion ofaddition, the mixture is heated to gentle reflux for 3 hours. Afterbeing cooled down, the flask is put in an ice-water bath. Water iscarefully added, and the mixture is stirred until the solid turnedwhite. After filtration, the solid is washed with additional ether, thefiltrate concentrated, and the residue dried in vacuo to yield theproduct as a white solid or sticky oil which can be used directly inacylation reactions without further purification.

2-Aminomethyl-2-isopropyl-3-methylbutan-1-ol: Yield 71%; ¹H NMR: δ 3.72(s, 2H), 2.93 (s, 2H), 2.65 (br.s, 3H), 1.97 (heptat, 2H, J=8.8 Hz),0.95 (d, 6H, J=8.5 Hz), 0.94 (d, 6H, J=9.0 Hz).

2-Aminomethyl-2-isobutyl-4-methylpentan-1-ol: Yield 75%; ¹H NMR: δ 3.54(s, 2H), 2.77 (s, 2H), 2.65 (br.s, 3H), 1.58-1.70 (m, 2H), 1.21 (d, 2H,J=7.0 Hz), 1.20 (d, 2H, J=7.5 Hz), 0.88 (d, 6H, J=8.0 Hz), 0.87 (d, 6H,J=8.5 Hz).

4-Aminopentan-2-ol

A 1000-mL round-bottom flask is charged with 3,5-dimethylisoxazole (9.7g, 0.1 mol) and water (200 ml). To this solution is added 1.0 M aqueouspotassium hydroxide (200 mL). Nickel-aluminum alloy (1:1, 32 g, 0.2 mol)is added in portions over 1 hour. After about another two hours, thereaction mixture is filtered over celite, and the solid washed withadditional water. The filtrate is extracted with methylene chlorideonce. The aqueous solution is acidified with concentrated HCl, andconcentrated to dryness. Potassium hydroxide (10 M, 5.0 ml) is added tothe residue, the mixture is extracted with methylene chloride, and theextract is dried with magnesium sulfate. After filtration, the filtrateis concentrated, the residue is dried in vacuo to yield 9.0 g (87%) ofthe product as a sticky oil, which is used directly in the followingacylation reaction. ¹H NMR (two isomers about 1:1.3): δ 4.10-4.18 (m,1Ha), 3.95-4.00 (m, 1Hb), 3.37-3.41 (m, 1Ha), 3.00-3.05 (m, 1Hb), 2.63(br.s, 3Ha+3Hb), 1.42-1.55 (m, 2Ha+1Hb), 1.12-1.24 (m, 6Ha+7Hb).

Acylated aminoalcohols

A 250-ml round bottom flask is charged with aminoalcohol (0.02 mol),pyridine (0.04 mol, 1.0 equiv.) and methylene chloride (50 ml). Theflask is immersed in an ice-water bath, and benzoyl chloride (0.04 mol,1.0 equiv.) is added dropwise. After the completion of addition, theflask is warmed up to room temperature, and the mixture is stirredovernight. Upon the completion of reaction monitored by GC, the mixtureis diluted with methylene chloride, and washed with water, saturatedammonium chloride, water, saturated sodium bicarbonate, and brine,consequently. The solution is dried over magnesium sulfate, filtered,and the filtrate concentrated. The residue is purified by flash columnchromatography to yield the product as a colorless oil or white solid.

¹H NMR data is obtained on a Brüker 500 MHz or 400 MHz NMR spectrometerusing CDCl₃ as solvent (in ppm).

Amide esters produced by the foregoing synthesis are provided in Table 1below.

TABLE 1 Halogenated Amide Esters Compound Structure ¹H NMR (CDCl₃ assolvent (in ppm) (1) 3-benzamido- 2,2-dimethylpropyl benzoate

Yield 88%; δ 8.08 (d, 2H, J = 8.5 Hz), 8.85 (d, 2H, J = 8.0 Hz),7.32-7.62 (m, 6H), 6.99 (t, 1H, J = 6.5 Hz), 4.23 (s, 2H), 3.38 (d, 2H,J = 6.5 Hz), 1.10 (s, 6H). (2) 4- benzamidopentan-2- yl benzoate

Yield 71% (two isomers with a ratio about 2.1 to 1); isomer 1: δ 7.96(dd, 2H, J = 10.5, 2.0 Hz), 7.68 (dd, 2H, J = 10.5, 1.5 Hz), 7.24-7.52(m, 6H), 6.67 (m, 1H), 5.25-5.34 (m, 1H), 4.27-4.38 (m, 1H), 1.90-2.02(m, 2H), 1.35 (d, 3H, J = 7.5 Hz), 1.27 (d, 3H, J = 7.5 Hz); isomer 2: δ8.05 (dd, 2H, J = 10.5, 2.0 Hz), 7.81 (dd, 2H, J = 10.0, 2.0 Hz),7.39-7.56 (m, 6H), 6.40 (d, 1H, J = 9.5 Hz), 5.22 (qt, 1H, J = 7.5, 8.0Hz), 4.28- 4.40 (m, 1H), 2.12 (ddd, 1H, J = 7.5, 11.0, 17.5 Hz), 1.81(ddd, 1H, J = 7.0, 8.5, 17.5 Hz), 1.44 (d, 3H, J = 8.0 Hz), 1.29 (d, 3H,J = 8.5 Hz). (3) 2- (benzamidomethyl)- 2-isopropyl-3- methylbutylbenzoate

Yield 68%; δ 7.95 (dd, 2H, J = 10.0, 2.0 Hz), 7.67 (dd, 2H, J = 10.0,2.0 Hz), 7.30-7.55 (m, 6H), 6.63 (t, 1H, J = 6.5 Hz), 4.38 (s, 2H), 3.57(d, 2H, J = 7.5 Hz), 2.06 (heptat, 2H, J = 8.5 Hz), 1.38-1.47 (m, 4H),1.04 (d, 12H, J = 8.5 Hz) (4) 2- (Benzamidomethyl)- 2-isobutyl-4-methylpentyl benzoate

Yield 71%; δ 8.02 (d, 2H, J = 9.5 Hz), 7.76 (d, 2H, J = 9.5 Hz),7.39-7.60 (m, 6H), 6.84 (t, 1H), J = 7.5 Hz), 4.30 (s, 2H), 3.47 (d, 2H,J = 8.0 Hz), 1.84 (heptat, 2H, J = 7.5 Hz), 1.38-1.47 (m, 4H), 0.96 (d,12H, J = 8.0 Hz). (5) 3-(4- fluorobenzamido)- 2,2-dimethylpropyl4-fluorobenzoate

Yield 86.5%; δ 8.08-8.15 (m, 2H), 7.82-7.90 (m, 2H), 7.10-7.18 (m, 4H),6.95-7.03 (m, 1H), 4.22 (s, 2H), 3.35 (d, 2H, J = 8.0 Hz), 1.09 (s, 6H).(6) 4-(4- Fluorobenzamido) pentan-2-yl 4- fluorobenzonate

Yield 73%, containing two isomers with a ratio about 3 to 2; δ 8.06 (dd,2Ha, J = 5.5, 9.0 Hz), 7.99 (dd, 2Hb, J = 5.5, 8.5 Hz), 7.83 (dd, 2Ha, J= 5.5, 8.5 Hz), 7.69 (dd, 2Hb, J = 5.5, 8.5 Hz), 7.01-7.15 (m, 4Ha +4Hb), 6.40 (d, 1Ha, J = 9.0 Hz), 6.14 (d, 1Hb, J = 9.0 Hz), 5.20-5.34(m, 1Hb), 5.18 (dt, 1Ha, J = 6.5, 6.0 Hz), 4.23-4.36 (m, 1Ha + 1Hb),2.02-2.12 (m, 1Ha + 1Hb), 1.958 (ddd, 1Hb, J = 4.0, 8.0, 15.0 Hz), 1.79(ddd, 1Ha, J = 5.5, 6.5, 14.0 Hz), 1.44 (d, 3Ha, J = 6.5 Hz), 1.41 (d,3Hb, J = 6.5 Hz), 1.34 (d, 3Hb, J = 6.5 Hz), 1.28 (d, 3Ha, J = 6.5 Hz).(7) 2-((4- Fluorobenzamido)methyl)- 2-isopropyl-3- methylbutyl 4-fluorobenzoate

Yield 80%; δ 8.04 (dd, 2H, J = 8.5, 5.5 Hz), 7.76 (dd, 2H, J = 8.5, 5.5Hz), 7.12 (dd, 2H, J = 8.5, 8.5 Hz), 7.09 (dd, 2H, J = 8.0, 9.0 Hz),6.52 (t, 1H, J = 6.0 Hz), 4.44 (s, 2H), 3.61 (d, 2H, J = 6.0 Hz), 1.85(heptat, 2H, J = 7.0 Hz), 1.10 (d, 6H, J = 7.0 Hz), 1.09 (d, 6H, J = 7.0Hz). (8) 2-((4- Fluorobenzamido)methyl)- 2-isobutyl-4- methylpentyl 4-fluorobenzoate

Yield 64%; δ 8.04-8.08 (m, 2H), 7.80-7.83 (m, 2H), 7.09-7.15 (m, 4H),6.79 (t, 1H, J = 6.5 Hz), 4.31 (s, 2H), 3.45 (d, 2H, J = 6.5 Hz), 1.85(heptat, 2H, J = 6.5 Hz), 1.38-1.46 (m, 4H), 0.99 (d, 12H, J = 6.5 Hz).(9) 3-(4- Chlorobenzamido)-2,2- dimethylpropyl 4- chlorobenzoate

Yield 80%; δ 8.00 (d, 2H, J = 11.0 Hz), 7.78 (d, 2H, J = 11.0 Hz), 7.45(d, 2H, J = 11.0 Hz), 7.42 (d, 2H, J = 11.0 Hz), 6.97 (t, 1H, J = 8.0Hz), 4.21 (s, 2H), 3.33 (d, 2H, J = 8.0 Hz), 1.08 (s, 6H). (10) 2-((4-Chlorobenzamido)methyl)- 2-isopropyl-3- methylbutyl 4- chlorobenzoate

Yield 80%; δ 7.94 (d, 2H, J = 10.5 Hz), 7.68 (d, 2H, J = 10.5 Hz), 7.42(d, 2H, J = 10.5 Hz), 7.39 (d, 2H, J = 10.5 Hz), 6.51 (t, 1H, J = 6.5Hz), 4.44 (s, 2H), 3.60 (d, 2H, J = 8.0 Hz), 2.08 (heptat, 2H, J = 8.8Hz), 1.09 (d, 6H, J = 8.5 Hz), 1.08 (d, 6H, J = 8.5 Hz). (11) 2-((4-Chlorobenzamido)methyl)- 2-isobutyl-4- methylpentyl 4- chlorobenzoate

Yield 65%; δ 7.97 (d, 2H, J = 8.5 Hz), 7.73 (d, 2H, J = 8.5 Hz), 7.43(d, 2H, J = 8.5 Hz), 7.41 (d, 2H, J = 8.5 Hz), 6.79 (t, 1H, J = 6.5 Hz),4.31 (s, 2H), 3.44 (d, 2H, J = 6.5 Hz), 1.85 (heptat, 2H, J = 6.0 Hz),1.38-1.46 (m, 4H), 0.99 (d, 12H, J = 7.0 Hz).

2. Procatalyst Preparation

A procatalyst precursor (according to the weight shown in Table 2) and2.52 mmol of internal electron donor (i.e., halogenated amide ester) arecharged into a flask equipped with mechanical stirring and with bottomfiltration. 60 ml of a mixed solvent of TiCl₄ and chlorobenzene (1/1 byvolume) is introduced into the flask. The mixture is heated to 115° C.and remains at the same temperature for 60 minutes with stirring at 250rpm before filtering off the liquid. 60 ml of mixed solvent is addedagain and the reaction is allowed to continue at the same desiredtemperature for 30 minutes with stirring followed by filtration. Thisprocess is repeated once. 70 ml of iso-octane is used to wash theresultant solid at ambient temperature. After the solvent is removed byfiltration, the solid is dried by N₂ flow or under vacuum.

TABLE 2 Procatalyst Precursor Weight MagTi-1 (M) 3.0 g SHAC ™ 310 (S)2.0 g

MagTi-1 is a mixed Mag/Ti precursor with a composition of Mg₃Ti(OEt)₈Cl₂(a MagTi precursor prepared according to example 1 in U.S. Pat. No.6,825,146) with an average particle size of 50 micron. SHAC™ 310 is abenzoate-containing catalyst (a BenMag procatalyst precursor with anaverage particle size of 27 micron) with ethyl benzoate as the internalelectron donor made according to Example 2 in U.S. Pat. No. 6,825,146,the entire content of which is incorporated herein by reference.Titanium content for each of the resultant procatalyst compositions islisted in Table 3. The peaks for internal donors are assigned accordingto retention time from GC analysis. No additional characterization isperformed.

TABLE 3 Procatalyst Compositions Procatalyst Compositions Internal EthylInternal Electron Procatalyst Pro- Ti Benzoate Electron Donor DonorPrecursor catalyst # (%) (%) (%) DiBP* MagTi-1 M-DiBP 2.99 0 12.49  1MagTi-1 M-1 3.32 0.45 trace SHAC ™ 310 S-1 3.07 1.08 trace 2 MagTi-1 M-23.27 0.53 trace 3 MagTi-1 M-3 3.14 0.17 2.98 SHAC ™ 310 S-3 3.53 0.931.92 4 MagTi-1 M-4 3.19 0.18 8.80 SHAC ™ 310 S-4 3.29 0.13 4.59 5MagTi-1 M-5 3.38 0 trace SHAC ™ 310 S-5 3.00 0.39 trace 6 MagTi-1 M-63.01 0 trace SHAC ™ 310 S-6 3.12 0.59 trace 7 MagTi-1 M-7 2.91 0 5.11SHAC ™ 310 S-7 3.25 0.62 5.33 8 MagTi-1 M-8 3.52 0 9.58 SHAC ™ 310 S-82.72 0.58 7.72 9 MagTi-1 M-9 5.32 0 trace SHAC ™ 310 S-9 2.81 2.89 Trace10  MagTi-1 M-10 3.47 0 1.58 SHAC ™ 310 S-10 3.16 0.99 6.96 11  MagTi-1M-11 3.97 0 1.80 SHAC ™ 310 S-11 2.72 0.37 6.97 *DiBP = diisobutylphthalate (comparative)

3. Polymerization

Polymerization is performed in liquid propylene in a 1-gallon autoclave.After conditioning, the reactors are charged with 1375 g of propyleneand a targeted amount of hydrogen and brought to 62° C. 0.25 mmol ofDCPDMS is added to 7.2 ml of a 0.27 M triethylaluminum solution inisooctane, followed by addition of a 5.0 wt % procatalyst slurry inmineral oil (actual solid weight is indicated in data tables below). Themixture is premixed at ambient temperature for 20 minutes before beinginjected into the reactor to initiate the polymerization. The premixedcatalyst components are flushed into the reactor with isooctane using ahigh pressure catalyst injection pump. After the exotherm, thetemperature is controlled to 67° C. Total polymerization time is 1 hour.

4. Polymer Testing

Polymer samples are tested for settled bulk density, melt flow rate(MFR), xylene solubles (XS), polydispersity index (PDI), and finalmelting point (T_(MF)). Unless specified, XS are measured using Viscotekmethod.

Halogenation of the amide ester improves catalyst productivity and/orpolymer properties for both of the SHAC™ 310 precursor and the MagTi-1precursor as shown in Table 4 below.

TABLE 4 Halogenated Amide Ester Catalyst Performance and PolymerProperties Internal Electron Procatalyst Pro-catalyst H₂ Activity XST_(MF) Donor Precursor Example # Pro-catalyst # (mg) (scc) (kg/g-hr) BDMFR (%) PDI (° C.) 1 MagTi-1 E-2** M-1 16.7 4500 8.2 0.29 4.0 4.50 8.24170.26 SHAC ™ 310 E-3** S-1 16.7 3000 12.8 0.35 1.2 3.50* 9.00 171.64 2MagTi-1 E-4** M-2 16.7 4500 32.0 0.33 3.5 3.37* 5.69 171.62 SHAC ™ 310E-5** S-2 8.4 3000 44.1 0.41 2.0 3.87* 5.89 171.58 3 MagTi-1 E-6** M-316.7 13500 12.6 0.27 12.0 2.34 7.50 171.32 SHAC ™ 310 E-7** S-3 16.713500 22.7 0.38 7.6 3.50 9.20 171.76 4 MagTi-1 E-8** M-4 16.7 13500 14.40.28 7.0 2.26 6.52 171.75 SHAC ™ 310 E-9** S-4 16.7 13500 35.7 0.39 5.63.84 7.82 171.86 5 MagTi-1 E-10 M-5 16.7 4500 7.7 0.35 8.1 5.02 7.81170.28 SHAC ™ 310 E-11 S-5 16.7 4500 19.9 0.37 3.7 5.16 9.61 170.30 6MagTi-1 E-12 M-6 8.4 1500 41.6 0.36 1.0 2.57 5.73 170.32 SHAC ™ 310 E-13S-6 8.4 3000 47.7 0.40 1.6 2.27 5.41 171.41 7 MagTi-1 E-14 M-7 16.7 10008.9 0.33 4.1 6.16 9.25 170.68 SHAC ™ 310 E-15 S-7 16.7 4500 30.5 0.391.0 3.67 9.21 171.73 8 MagTi-1 E-16 M-8 8.4 4500 24.7 0.34 1.7 5.64 8.32170.82 SHAC ™ 310 E-17 S-8 8.4 13500 51.8 0.39 2.2 2.49 7.72 171.44 9MagTi-1 E-18 M-9 16.7 1500 5.7 0.29 12.7 9.74 6.98 169.03 SHAC ™ 310E-19 S-9 8.4 4500 33.3 0.37 3.5 4.77 8.84 170.67 10 MagTi-1 E-20 M-1016.7 1500 7.6 0.34 3.7 6.15 9.27 169.90 SHAC ™ 310 E-21 S-10 8.4 1350034.3 0.38 5.0 2.87 8.66 171.56 11 MagTi-1 E-22 M-11 16.7 1500 8.6 0.292.9 7.45 8.46 170.11 SHAC ™ 310 E-23 S-11 16.7 13500 37.4 0.37 3.1 1.587.02 171.93 *XS by NMR method **Comparative sample BD = bulk density EED= DCPDMS for all polymers in Table 4

MWD is broadened using halogenated amide esters as internal electrondonors compared to conventional DiBP procatalyst. Utilization of aBenMag procatalyst precursor, (i.e., SHAC™ 310), significantly improvesthe catalyst activity and XS while maintaining a broad MWD for acorresponding EED.

Procatalysts made from the halogenated amide ester internal donors andSHAC™ 310 precursor show high catalyst activity, lower XS, and higherTMF. Furthermore, the PDI of the resultant polymer is markedly higherthat what can be achieved using DCPDMS with the DiBP-based procatalyst.

5. External Electron Donor

TABLE 5 Effect of EEDs on Catalyst Performance and Polymer PropertiesPro- Procatalyst H₂ Activity XS T_(MF) IED Example # catalyst # (mg) SCA(scc) (kg/g-hr) BD MF (%) PDI (° C.) DiBP E-1** M-DiBP 16.7 DCPDMS 150028.6 0.4 2.5 2.98 4.81 171.48 DiBP E-58** M-DiBP-B 4.8 MChDMS 1500 20.00.39 4.0 3.03 4.13 170.43 DiBP E-66** M-DiBP-B 16.7 BTMSMDMS 500 17.20.32 4.3 8.57 5.93 168.89 DiBP E-59** M-DiBP 16.7 NPTMS 1000 29.5 0.393.4 2.55 3.92 170.00 DiBP E-60** M-DiBP-B 16.7 TEOS 200 11.9 0.31 2.67.79 4.77 168.57 DiBP E-61** M-DiBP-B 16.7 MMBCHC 2000 11.1 0.3 4.1 3.606.35 170.23 DiBP E-62** M-DiBP-B 16.7 BMMDMH 1500 22.9 0.36 5.7 2.413.92 170.13 DiBP E-63** M-DiBP-B 16.7 PDODMB 2000 9.9 0.27 5.6 6.99 6.99169.73 DiBP E-64** M-DiBP-B 16.7 TEP 200 11.5 0.31 3.1 7.21 4.53 167.87DiBP E-65** M-DiBP-B 16.7 TMPY 1500 26.9 0.37 3.8 5.71 4.90 170.21 1E-67** M-1 33.4 DCPDMS 6000 6.5 0.31 7.0 4.4 8.54 170.65 1 E-68** M-133.4 MChDMS 4500 4.7 0.33 5.6 5.86 8.70 170.18 1 E-73** M-1 33.4BTMSMDMS 3000 5.8 0.28 4.2 8.95 12.10 169.70 1 E-69** M-1 33.4 TEOS 30004.1 0.3 5.8 6.98 10.63 169.88 1 E-70** M-1 33.4 MMBCHC 6000 2.8 0.28 2.33.44 9.63 1 E-71** M-1 33.4 PDODMB 6000 3.6 0.27 3.8 4.21 9.18 170.79 1E-72** M-1 33.4 TEP 3000 4.6 0.29 4.6 6.80 11.56 169.58 1 E-3** S-1 16.7DCPDMS 3000 12.8 0.35 1.2 3.50* 9.00 171.64 1 E-74** S-1 16.7 NPTMS 600011.6 0.34 10.7 4.75* 8.72 170.12 8 E-17 S-8 8.4 DCPDMS 13500 48.0 0.392.2 2.49 7.72 171.44 8 E-75 S-8 8.4 DIPDMS 15000 34.9 0.39 5.9 2.75 7.76170.44 8 E-76 S-8 16.7 MCHDMS 9000 23.7 0.39 1.6 2.64 7.37 171.76 8 E-85S-8 16.7 BTMSMDMS 9000 24.6 0.37 1.7 5.01 10.18 170.88 8 E-77 S-8 16.7NPTMS 9000 29.8 0.39 1.2 1.87 8.74 171.23 8 E-78 S-8 8.4 PTES 9000 38.60.39 2.2 3.03 8.57 170.41 8 E-79 S-8 16.7 TEOS 20000 12.2 0.36 6.4 2.619.26 171.45 8 E-80 S-8 16.7 MMBCHC 9000 12.4 0.39 0.7 1.61 7.95 172.27 8E-81 S-8 16.7 BMMDMH 9000 14.5 0.39 3.4 2.74 8.50 171.57 8 E-82 S-8 16.7PDODMB 9000 16.7 0.4 0.9 2.06 8.33 171.63 8 E-83 S-8 16.7 TEP 9000 20.50.38 2.3 2.87 9.56 170.64 8 E-84 S-8 16.7 TMPY 9000 20.7 0.36 5.0 5.8910.48 170.56 *XS by NMR method **Comparative example DCPDMS =dicyclopentyldimethoxysilane MChDMS = methylcyclohexyldimethoxysilaneBTMSMDMS = bis(trimethylsilylmethyl)dimethoxysilane NPTMS =n-propyltrimethoxysilane TMPY = 2,2,6,6-tetramethylpiperidine TEOS =tetraethoxysilane MMBCHC = methyl1-methoxybicyclo[2.2.1]-hept-5-ene-2-carboxylate BMMDMH =3,3-bis(methoxymethyl)-2,5-dimethylhexane PDODMP = 2,4-pentanedioldi(2-methylbenzoate) TEP = triethyl phosphite

Many EEDs that are not useful with a DiBP-based procatalyst due to lowtacticity (high XS) are suitable for use with a halogenated amideester-based procatalyst. Surprisingly, the effect of EEDs on the PDI forthe halogenated amide ester procatalysts are different than the effectof the same EED when used with a DiBP-based procatalyst. For example,the PDI value for polypropylene produced from DiBP procatalyst usingTEOS, BMMDMH, and TEP as EED is lower than the PDI value forpolypropylene produced with DiBP procatalyst using DCPDMS as EED. Incontrast, the PDI value for polypropylene produced from the halogenatedamide ester procatalyst using these same EEDs is greater than the PDIvalue for polypropylene produced with the DiBP procatalyst using DCPDMSas EED. The effect on XS is also different. The non-alkoxysilane EEDslead to high XS with the DiBP-based procatalyst, while the samenon-alkoxysilane EEDs exhibit low XS with the halogenated amide esterprocatalyst (Table 5). Low XS is a basic requirement for many polymerend-use applications. In addition, applicants have surprisinglydiscovered that EEDs, in particular, the non-silane EEDs, expand theapplication potential for the halogenated amide ester catalysts andresultant polymers. As shown in Table 5 above, EEDs may be used tomanipulate polymer properties and broaden the property variation rangeof halogenated amide ester-based procatalysts.

TABLE 6 Effect of EED/ALA on Catalyst Performance and Polymer Propertiesfor Halogenated Amide Ester Catalyst Pro- Procatalyst H₂ Activity XST_(MF) IED Ex # catalyst # (mg) SCA (scc) (kg/g-hr) BD MF (%) PDI (° C.)8 E-86 S-8 8.4 C/IPM 5/95 9000 46.8 0.38 1.6 3.32 7.97 171.15 8 E-87 S-88.4 D/IPM 40/60 9000 46.1 0.39 1.1 3.19 7.59 171.95 8 E-88 S-8 8.4 N/IPM10/90 9000 26.9 0.38 1.0 3.05 8.45 171.94 8 E-89 S-8 8.4 D/TMPnDODBz20000 42.9 0.39 3.1 1.85 8.28 171.22 10/90 8 E-90 S-8 8.4 D/PTES/IPM9000 47.5 0.38 2.7 3.51 8.42 171.71 12/28/60 C = MChDMS N = NPTMS PTES =propyltriethoxysilane D = DCPDMS IPM = isopropyl myristate TMPnDODBz =2,2,4-trimethyl-1,3-pentanediol Dibenzoate

Introduction of ALAs into the polymerization reaction enhances processoperability by rendering the self-limiting property to the catalystsystem. Carboxylate esters, such as isopropyl myristate (IPM) and2,2,4-trimethyl-1,3-pentanediol dibenzoate (TMPnDODBz) are suitableself-limiting agents. When an EED/ALA mixture is used with thehalogenated amide ester-based procatalyst, the catalyst shows highcatalyst activity and the resultant polymer shows low XS, high PDI, andhigh T_(MF) (Table 6). EEDs may also be used alone or in combinationwith an ALA.

High catalyst activity, low XS, high PDI, and high T_(MF) are obtainedusing the halogenated amide ester procatalyst with a variety of EEDsalone or in combination with an ALA.

It is specifically intended that the present disclosure not be limitedto the embodiments and illustrations contained herein, but includemodified forms of those embodiments including portions of theembodiments and combinations of elements of different embodiments ascome within the scope of the following claims.

The invention claimed is:
 1. A halogenated amide ester having thestructure (I):

wherein R₁-R₆ are the same or different, each of R₁-R₆ is selected froma group consisting of hydrogen, a halogen, and an acyclic alkyl grouphaving 1-20 carbon atoms, and at least one of R₁-R₆ is an acyclic alkylgroup; and Ar₁ and Ar₂ are the same or different and each of Ar₁ and Ar₂is selected from a group consisting of an aryl group having 6-20 carbonatoms and an arylalkyl group having 7-20 carbon atoms, and at least oneof Ar₁ and Ar₂ is halogenated.
 2. The halogenated amide ester of claim1, wherein each of Ar₁ and Ar₂ is selected from the group consisting ofa phenyl group, a naphthyl group, an anthracenyl group, and aphenanthrenyl group.
 3. The halogenated amide ester of claim 1, whereinat least two of R₁-R₆ are an acyclic alkyl group having 1-6 carbonatoms.
 4. The halogenated amide ester of claim 1 having the structure(II)

wherein R₁₁-R₁₃ and R₂₁-R₂₃ are hydrogen, and at least one of R₁₁-R₁₃and at least one of R₂₁-R₂₃ is a halogen.
 5. The halogenated amide esterof claim 4, wherein each of R₁₂ and R₂₂ is selected from the groupconsisting of chlorine and fluorine.
 6. The halogenated amide ester ofclaim 1, wherein each of R₁ and R₂ is a hydrocarbyl group having 1 to 6carbon atoms.
 7. The halogenated amide ester of claim 1, wherein each ofR₃ and R₅ is a hydrocarbyl group having 1 to 6 carbon atoms.
 8. Aprocatalyst composition comprising: a combination of a magnesium moiety,a titanium moiety and an internal electron donor comprising ahalogenated amide ester of structure (I):

wherein R₁-R₆ are the same or different, each of R₁-R₆ is selected froma group consisting of hydrogen, a halogen, a hydrocarbyl group having1-20 carbon atoms, and a substituted hydrocarbyl group having 1-20carbon atoms; and Ar₁ and Ar₂ are the same or different and each of Ar₁and Ar₂ is selected from a group consisting of an aryl group having 6-20carbon atoms and an arylalkyl group having 7-20 carbon atoms, and atleast one of Ar₁ and Ar₂ is halogenated.
 9. The procatalyst compositionof claim 8 comprising a benzoate.
 10. A catalyst composition comprising;a procatalyst composition of claim 8; and a cocatalyst.
 11. The catalystcomposition of claim 10 comprising an external electron donor selectedfrom the group consisting of a silicon compound, a bidentate compound, adiether, a diol ester, a carboxylate, an amine, a phosphite, andcombinations thereof.
 12. The catalyst composition of claim 10comprising an activity limiting agent selected from the group consistingof a carboxylic acid ester, a diether, a diol ester, and combinationsthereof.
 13. A process for producing an olefin-based polymer comprising:contacting, under polymerization conditions, an olefin with a catalystcomposition comprising a halogenated amide ester of structure (I):

wherein R₁-R₆ are the same or different, each of R₁-R₆ is selected froma group consisting of hydrogen, a halogen, a hydrocarbyl group having1-20 carbon atoms, and a substituted hydrocarbyl group having 1-20carbon atoms; and Ar₁ and Ar₂ are the same or different and each of Ar₁and Ar₂ is selected from a group consisting of an aryl group having 6-20carbon atoms and an arylalkyl group having 7-20 carbon atoms, and atleast one of Ar₁ and Ar₂ is halogenate; and forming an olefin-basedpolymer comprising the halogenated amide ester.
 14. The process of claim13 wherein the olefin is propylene and the process comprises forming apropylene-based polymer having a polydispersity index of from about 5.0to about 20.0.